Cyclopentadienyl manganese tricarbonyl sulfones



United States Patent 3,317,572 CYCLOPENTADIENYL MANGANESE TRICARBONYL SULFONES John Kozikowski, Walled Lake, Mich., and Michael Cais,

Haifa, Israel, assignors to Ethyl Corporation, New

action:

. York, N.Y., a corporation of Virginia 5 \l/ VSOZR ZX N0 Drawing. Original application Aug. 12, 1960, Ser.

1 451,135. lgividl'ed and this application May 13, Mnwoh MMCO" 42 In the above reaction, R is an alkyl or aralkyl group, and 2 Clams' (CL 260-429) X is a halogen. The reaction conditions employed are This application is a division of application not critical and the alkyl or aralkyl halide, when used in 49,135, filed Aug. 12, 1960, now abando d, sutficlent excess, may itself serve as the solvent. To fur- This invention relates to a variety of organometallic ther illustrate this form of our invention, there is presented compounds and the processes employed in their producthe 'fonowlhg general P and tables which 3 fion' More ifi ll this invention relates to marize the results obtained from several such reactions. pounds and processes involving the use of a cyclopenta- Exam I8 I dienyl sulfonic acid manganese tricarbonyl compound. p

A bj f our invention is to provide new organo The sodium salt derivative of cyclopentadienyl sulfinic metallic compounds and processes for their preparation. acid manganese tricarbonyl Was dissolved in ethanol and A further object is to provide cyclopentadienyl manganese 2O r fluxed with a slight excess of the alkyl or aralkyl halide. tricarbonyl derivatives and processes for their preparation. The Cooled mixture Was filtered to remove the Sodium Additional objects become apparent fr m a reading WhlCh formed, and the ethanolic filtrate was COl'lCEIlof the specification and claims which follow. {rated y heating until crystals began to pp After The objects of this invention are accomplished by pro- Cooling, the Crystals Were Collected and Were generally of viding cyclopentadienyl manganese tricarbonyl sulfones a high degree of y- An additional p of crystals such as {{[(tricarbonylmanganese)cyclopentadienyncarcould be obtained by diluting the ethanolic mother liquor bonylmethylsulfonyl}cyclopentadienyl}manganese tricarwith Wateh bonyl, and a process for preparing ame, The Following the general procedure set forth in the prepounds are formed by reacting a cyclopentadienyl sulfinic ceding example, the results Were Obtained as Set f h in acid manganese tricarbonyl with an alkali metal hydroxide the following Table The analysis Obtained fer the or an alkali metal salt of an acid which is weaker than p unds of Table I are Set forth in Table 11.

TABLE I Reflux Yield Recrystn. R-X lililllge, Compound Obtained Percent M.P., C. Solvent CHaI 2 [(Methylsulfonyl) cyclopentadienyl] manganese tricarbonyl 97 156-158 B *1 C1CH2KCH3 3C12C5H2OH 20 [(3,5di-tert-butyl-4-hydroxybenzylsulfonyl) cyclopentadienyHmanga- 84 170-171 EB CHBCOOH2C1 2' [(i i gzio i iifi h igz h gl cyclopentadienyl] manganese tricarbonyl 75 123-124 B BrCHiCOC5H4Mn(CO) 3 {{[(Tricarbonylmanganese) cyclopentadienyl] carbonyl methylsul- 94 167-168 E/B fonyl} cyclopentadienyl} manganese tricarbonyl.

B-benzene; E-ethanol.

b 2,G-di-tert-bntyl-a-chloro-p-cresol. a The 2,4-dinitrophenylhydrazone of (from chloroform/methanol).

d (Brornoacetylcyclopentadienyl) manganese tricarbonyl.

[(p-methoxyphenylsnli'onyl)cyclopentadienyl] manganese tricarbonyl formed very readily, m.p. 190-191 Analysis, caled. i'or C|7Hi3MnN4O0S: C, 40.4; H, 2.57; Mn, 10.9. Found: C, 40.5; H, 2.60; Mn, 10.9.

the cyclopentadienyl sulfinic acid manganese tricarbonyl reactant. As a result, there is formed a salt having the formula SOzZ R. Mn(CO):

in which R is a univalent hydrocarbon group containing from one to eight carbon atoms, x is an integer ranging from zero to three, and Z is an alkali metal. The intermediate salt is then reacted with an alkyl halide or an aralkyl halide which may be substituted or unsubstituted.

. TABLE II Compounds Carbon Percent .Hydrogen Percent Manganese Percent Sulfur Percent Calcd. Found Calcd. Found Calcd Found Calcd. Found [(Methylsulionyl) cyclopentadienyl] manganese tricarbonyl 38. 3 37. 9 2. 50 2. 42 19. 4 19.4 11.3 11. 6 [(3.5di-tert-butyl-4-hydroxybenzylsulfonyl) cyclopentadienyl] manganese tricarbonyl 56. 8 56. 8 5. 63 5. 66 11.3 11.3 6. 6 6. 6 [(Acetonylsulionyl) cyclopentadienyl] manganese tricarbony 16.9 16.9 [(Tricarbonylinanganese) cyclopentadienyl] carbonyl methylsulionyl} cyclopentadienyl} manganese tricarbonyl- 42.1 42. 2 1. 2.19 21. 4 21. 5 6. 28 6. 24

Bromoacetylcyclopentadienyl manganese tricarbonyl, which was employed as a reactant, as reported in Table I, was prepared by reacting an acylcyclopentadienyl manganese tricarbonyl compound having the formula in which R is a univalent hydrocarbon radical containing from one to about eight carbon atoms and x is an integer ranging from zero to three, with a halogenating agent. In the specific case of the bromoacetyl compound, the halogenating agent was bromine. Analogous compounds such as the chloroacetylcyclopentadienyl manganese tricarbonyl and iodoacetylcyclopentadienyl manganese tricarbonyl compounds are prepared by reaction of chlorine or iodine with an acetylcyclopentadienyl manganese tricarbonyl compound. The reaction can be conducted in any inert solvent, although preferably, the solvent is polar and most preferably, it is an ether. The reaction is conducted at low temperature in the order of about C. To illustrate the reaction, there is presented the following example.

Example [I To a solution comprising 24.6 grams of acetylcyclo-- pentadienyl manganese tricarbonyl in 250 ml. of ether cooled to 0 C. was added 16.0 grams of bromine. The bromine was added dropwise with stirring over a one-half hour period. Stirring was continued for an additional onehalf hour after which the ether and hydrogen bromide were removed by distillation of the reaction mixture at reduced pressure. The yellow-orange compound (bromo acetylcyclopentadienyl manganese tricarbonyl) which remained was recrystallized from ether and was found to be soluble in organic solvents. The yieldwas 27 grams of bromoacetylcyclopentadienyl manganese tricarbonyl or 83 percent of theory. The compound had a melting point of 7577 C. and on analysis there was found: C, 37.1; H, 1.93; Mn, 17.0; Br, 24.8 percent. Calculated for C H MnO Br: C, 36.9; H, 1.85; Mn, 16.9; Br, 24.6 percent.

A further embodiment of our invention concerns reaction of compounds having the formula:

These compounds are made, as in the case of the {{[(tricarbonylmanganese)cyclopentadienyl]carbonylmethylsulfonyl}cyclopentadienyl}manganese tricarbonyl reported in Tables I and II, from reaction of the alkali metal salt of a cyclopentadienyl sulfinic acid manganese tricarbonyl with an appropriate haloacylcyclopentadienyl manganese tricarbonyl compound. In the above formula, the group R is a univalent hydrocarbon group, the group R is a divalent hydrocarbon group, and R" is hydrogen or R, each hydrocarbon group containing from one to about eight carbon atoms, x is an integer ranging from zero to three, and y is either zero or one. The above compounds are reacted with a base such as sodium hydroxide and a hydroxyl-containing solvent such as water or an alcohol such as ethanol to form a [(hydrocarbylsulfone) cyclopentadienyl]manganese tricarbonyl and the alkali metal salt of a cyclopentadienylcarboxylic acid manganese tricarbonyl. These compounds have the respective formulae:

SO:R,OH

GMn(CO)| R.

and

Ryi JOM .T

In the latter Formula II, M is an alkali metal.

In Formulae I and II, R is a hydrocarbon group containing from one to about eight carbon atoms, x is an integer ranging from zero to three, and y is either zero or one.

The alkali metal salt of the cyclopentadienyl carboxylic acid manganese tricarbonyl is readily separated from the cyclopentadienyl sulfone manganese tricarbonyl compound by means of extraction. The alkali metal salt is then acidified to form the carboxylic acid compound which is insoluble in an aqueous medium and can be filtered off.

To further illustrate this embodiment of our invention, there is presented the following example.

Example IIl Four grams of {{[(tricarbonylmanganese)cyclopentadienyl] carbonylmethylsulfonyl}cyclopentadienyl}manganese tricarbonyl, two grams of potassium hydroxide, 50 ml. of ethanol and 20 ml. of water were refluxed for 15 hours, cooled and poured into 400 ml. of water. Crystalline plates separated out and were filtered to yield 1.5 grams of a solid which was identified as [(methylsulfonyl) cyclopentadienyl] manganese tricarbonyl.

The aqueous filtrate was acidified with hydrochloric acid and the solid which precipitated was filtered off. The solid precipitate was recrystallized from benzene to give 1.8 grams (93 percent yield) of cyclopentadienyl carboxylic acid manganese tricarbonyl as yellow needle-like crystals having a melting point of 194-195 C. The compound was identified by means of its infrared spectrum and analysis. Found: Mn, 22.1 percent. Calculated: Mn, 22.2 percent.

The preparation of cyclopentadienyl sulfinic acid manganese tricarbonyl and related compounds is fully described in our copending application Ser. No. 283,139, filed May 13, 1963, now US. 3,205,245, issued Sept. 7, 1965.

Among the important uses of our compounds is their use as fuel and oil additives. For example, they are useful antiknocks when added to gasoline. They may be used as primary antiknocks in which they are the major antiknock component in the fuel or as supplemental antiknocks. When used as supplemental antiknocks, they are present as the minor antiknock component in the fuel in addition to a primary antiknock such as a tetraalkyllead compound. Typical alkyllead compounds are tetraethyllead, tetrabutyllead, tetramethyllead and various mixed lead alkyls such as dimethyldiethyllead, diethyldibutyllead and the like. When used as either a supplemental or primary antiknock, our compounds may be present in the gasoline in combination with typical scavengers such as ethylene dichloride, ethylene dibromide, tricresylphosphate, trimethylphosphate and the like.

The compounds of our invention have further utility as additives to residual and distillate fuels generally, e.g., jet fuels, home heater fuels and diesel fuels, to reduce smoke and/or soot formation. Also, they may be employed as additives to lubricating oils in which case they act to improve the lubricity of the base oil.

Our compounds are further useful in many metal plating applications. In order to effect metal plating using the compounds, they are decomposed in an evacuated space containing the object to be plated. On decomposition, they lay down a film of metal on the object. The gaseous plating may be carried out in the presence of an inert gas so as to prevent oxidation of the plating metal or the object to be plated during the plating operations.

The gaseous plating technique described above finds Wide application in forming coatings which are not only decorative but also protect the underlying substrate material.

Deposition of metal on a glass cloth illustrates the applied process. A glass cloth band weighing one gram is dried for one hour in an oven at C. It is then placed in a tube which is devoid of air and there is added to, the tube 0.5 gram of [(methylsulfonyl)cyclopentadienylJmanganese tricarbonyl. The tube is heated at 400 C. for one hour after which time it is cooled and opened. The cloth has a uniform metallic grey appearance and exhibits a gain in weight of about 0.02 gram.

A further utility for our compounds is as drying agents in which case the compounds are incorporated in paints, varnish, printing inks, synthetic resins of the drying oil type, oil enamels and the like. A still further utility for our compounds is their use as chemical intermediates in the preparation of metal-containing polymeric materials or in the preparation of new organic materials.

Having fully defined the novel compounds of our invention, their mode of preparation and their many utilities, We desire to be limited only within the lawful scope of the appended claims.

We claim:

1. {{[(Tricarbonylmanganese) cyclopentadienyl] carbonylmethylsulfonyl}cyclopentadienyl}manganese tricarwith a base and a hydroxyl-containing solvent.

No references cited.

TOBIAS E. LEVOW, Primary Examiner. A. P. DEMERS, Assistant Examiner. 

1. ((((TRICARBONYLMANGANESE) CYCLOPENTADIENYL) CARBONYLMETHYLSULFONYL)CYCLOPENTADIENY)MANGANESE TRICARBONYL. 